Single-crystal 2D covalent organic frameworks for high-capacity methane storage.

Yu, Baoqiu; Oliveira, Felipe L; Li, Wenliang; Xu, Qingmei; Ding, Xu; Yuan, Shangwei; Jin, Yucheng; Liu, Hua et al. · Nat Commun · 2026

basic_science · Level V

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Abstract

2D covalent organic frameworks (COFs) usually possess a polycrystalline nature as well as lower porosity and surface area than 3D counterparts, restraining their exploration over gas storage applications. Herein, a substituent strategy has been proposed and employed to generate three robust single-crystal 2D COFs isomers with atom-resolution structures determined by 3D electron diffraction. Among three isomers, a precise engineering of their interlayer distance affords the highest Brunauer-Emmett-Teller surface area of ~2100 m<sup>2</sup> g<sup>-1</sup> and the largest pore volume of 1.40 cm<sup>3</sup> g<sup>-1</sup> for the desolvated GZU-1. This COF shows the highest total volumetric methane uptake of 240 cm<sup>3</sup> (STP) cm<sup>-3</sup> at 273 K and 100 bar among 2D COFs, even comparable with those for excellent 3D MOFs. This work not only delivers unique insight into the design of 2D single-crystal COFs by interlayer stacking regulation, but also promotes the application of highly porous 2D COFs in gas storage.